US4177054A - 1,2,3-Thiadiazole-5-carboxylic acid derivatives, herbicidal and growth regulating compositions containing the same and process for making same - Google Patents

1,2,3-Thiadiazole-5-carboxylic acid derivatives, herbicidal and growth regulating compositions containing the same and process for making same Download PDF

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US4177054A
US4177054A US05/918,462 US91846278A US4177054A US 4177054 A US4177054 A US 4177054A US 91846278 A US91846278 A US 91846278A US 4177054 A US4177054 A US 4177054A
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thiadiazole
methyl
carboxylic acid
compound
substituted
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US05/918,462
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Friedrich Arndt
Hans-Rudolf Kruger
Reinhart Rusch
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Bayer Pharma AG
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Schering AG
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/06—1,2,3-Thiadiazoles; Hydrogenated 1,2,3-thiadiazoles

Definitions

  • the invention relates to 1,2,3-thiadiazole-5-carboxylic acid derivatives having a herbicidal and growth regulating activity and compositions containing the same.
  • Effective weed suppression in agricultural production has three essential functions: it must insure the growth of the crops it must assure the usefulness of the products harvested, and it must improve the working and production conditions.
  • Effective weed suppression frequently constitutes the condition precedent to complete mechanization of a line of operation such as for instance grain, maize or beet planting, or form the basis for introducing new agricultural working methods and seeding processes, as for instance the direct speed process in case of maize, grain, soybean and cotton.
  • An object of the present invention is therefore the provision of an agent which permits an improvement of the weed suppression techniques.
  • R 1 is hydrogen or is alkyl of which the chain may be interrupted in one or several places by oxygen or sulfur and which may be substituted by halogen and in which
  • X constitutes (a) the residue --Y--R 2 in which R 2 is hydrogen, alkyl, which may be substituted, aryl, which may also be substituted, aryl-C 1 -C 2 -alkyl which may also be substituted, or constitutes a univalent metal equivalent and wherein
  • Y is oxygen or sulfur, or wherein
  • X constitutes (b) the residue ##STR4## in which R 3 and R 4 are the same or different and may be hydrogen, C 1 -C 18 alkyl which may also be substituted, C 2 -C 8 -alkenyl or alkinyl, aryl-C 1 -C 3 -alkyl which may also be substituted, a C 3 -C 8 -cycloaliphatic hydrocarbon residue which may also be substituted, C 3 -C 8 -cycloalkyl-C 1 -C 3 -alkyl- which may also be substituted, an aromatic hydrocarbon residue which may be substituted in one or several places by C 1 -C 6 -alkyl and/or halogen and/or C 1 -C 6 -alkoxy and/or nitro and/or trifluoromethyl or wherein R 3 and R 4 together with the adjoining nitrogen atom constitute a morpholino- piperidino- or pyrrolidino group.
  • the compounds of the invention are characterized by a soil- and/or leaf-herbicidal activity against seed weeds and resistant weeds. Their activity is partly systemic. They are particularly effective against dicotyl and monocotyl weed types of the families Digitalis, Trifolium, Portulaca, Papaver, Daucus, Kochia, Gypsophyla, Lactuca, Solanum, Escholtzia, Cheiranthus, Phacelia, Euphorbia, Linum, Convolvulus, Brassica, Datura, Cichorium, Ipomoea, Setaria, Agrostis, Phleum, Alopecurus, Phalaris, Dactylis, Festuca, Arrhenaterum, Lolium, Bromus, Avena, Allium, Cucumis, Medicago, Stellaria, Senecio, Matricaria, Lamium, Centaurea, Amaranthus, Galium, Chrysanthemum, Polygonum, Sorghum, Alopecurus, E
  • a selective application is possible for instance in grain, cotton, soybean and plantation cultures.
  • the highest activities are displayed by these agents, if they are sprayed onto a preexisting weed growth or are sprayed prior to the emergence.
  • the so-called seed cultures can also be drilled a few days after spraying.
  • the individual compounds of the present invention may also modify the natural development of the plants so as to obtain various properties which may be agriculturally or horticulturally valuable.
  • the application of the compounds of the invention can be effected onto seeds or seedlings prior to or after emergence, onto roots, stems, leaves, blossoms, fruits or other plant parts.
  • the modification of the natural growth normally can be ascertained visually by changes of growth, of shape, of color or of structure of the treated plant or any of its parts.
  • the compounds of the invention surprisingly, meet all functions necessary for an improvement of the weed suppression technique to an extent heretofore unknown.
  • R 1 is hydrogen or C 1 -C 4 -alkyl which may be substituted by chlorine or bromine, for instance methyl, propyl, chloromethyl or bromomethyl,
  • R 2 is hydrogen or C 1 -C 4 -alkyl, for instance methyl, ethyl, propyl, isopropyl, butyl, or is an aromatic hydrocarbon such as phenyl, 4-chlorophenyl, 4-nitrophenyl, 3-chlorophenyl, 2-chlorophenyl or 4-methylphenyl, or is an alkali metal atom, preferably lithium, sodium or potassium, or is a corresponding equivalent of a bivalent metal, for instance zinc, manganese, calcium, magnesium or barium, and wherein
  • R 3 and R 4 are the same or different and may be hydrogen, C 1 -C 8 alkyl which may be substituted by halogen, phenoxy, dialkylamino, alkoxy, alkoxycarbonyl, C 2 -C 6 alkenyl or alkinyl, C 3 -C 8 -cycloalkylmethyl which may also be substituted, C 6 -C 8 cycloalkyl which may also be substituted, or wherein R 3 and R 4 may be phenyl, chlorophenyl, nitrophenyl or methylphenyl.
  • the residues identified as R 3 and R 4 may for instance be hydrogen, or in case of C 1 -C 18 alkyl may be methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, 2,2-dimethyl-1-propyl, n-heptyl, n-nonyl, n-undecyl, n-octadecyl, 3-methylbutyl, 4-methyl-2-pentyl, isobutyl, 3,3-dimethylbutyl, 2-butyl or 3,3-dimethyl-2-butyl, or in case of C 1 -C 18 , alkyl may be 2-chloroethyl, 3-chloropropyl, 3-bromopropyl, 2-bromoethyl, 1-phenoxy-2-propyl, 3-dimethylaminopropyl, 2-dimethylaminoethyl, 3-diethylaminoprop
  • the compounds of the invention can be used either individually, or in mixture with each other or in mixture with other agents.
  • herbicidal agents there may for instance be added to the compounds of the invention the following herbicidal agents:
  • chlorates preferably calcium chlorate, potassium chlorate, magnesium chlorate or sodium chlorate,
  • non-phytotoxic additives which in herbicides result in a synergistic increase of the activity and furthermore they can be used as wetting agents, emulsifiers, solvents and oily additives.
  • the compounds of the invention or their mixture are preferably used in the form of compositions such as powders, dusting agents, granulates, solutions, emulsions or suspensions.
  • liquid and/or solid carrier materials or diluents and, if desired, wetting agents, adhesion promotion agents, emulsifiers and/or dispersing agents.
  • Suitable liquid carrier materials are, for instance, water, aliphatic and aromatic hydrocarbons, cyclohexanone, isophorone, dimethylsulfoxide, dimethylformamide, and furthermore mineral oil fractions.
  • solid carrier materials there can be used mineral earths, for instance, tonsil, silicagel, talc, kaolin, attaclay, limestone, silicic acid, and plant products, for instance, flours.
  • mineral earths for instance, tonsil, silicagel, talc, kaolin, attaclay, limestone, silicic acid, and plant products, for instance, flours.
  • surface active agents for instance calciumlignosulfonate, polyoxyethylene-alkylphenylether, naphthalenesulfonic acids and their salts, phenolsulfonic acid and their salts, formaldehyde condensation products, fatty alcohol sulfates, as well as substituted benzosulfonic acids and their salts.
  • the proportion of the active agent or agents can be varied in the different compositions within a broad range.
  • the compositions may, for instance, contain about 10 to 80% by weight of active agents, 90 to 20% by weight of liquid or solid carrier materials and, if desired, up to 20% by weight of surface active agents in which case a corresponding reduction of the carrier materials is effected.
  • the application of the compounds of the invention and of the composition can be effected in conventional form, for instance with water as carrier materials in spray amounts of about 100 to 1000 liters to about 2.5 acres.
  • the application of the agents is possible in the so-called “low-volume” and “ultra-low-volume” process as well as in the form of so-called microgranulates.
  • the new herbicides and growth regulating agents can be made in different ways.
  • R 1 , R 2 , R 3 , R 4 , X and Y have the same meaning as in the above formula I, Z is halogen, preferably chlorine, and R 5 is C 1 -C 4 -alkoxy.
  • the reaction in all of these cases is carried out at a temperature between about 0° and 120° C. Preferred is a temperature between room temperature and the reflux temperature of the particular reaction mixture.
  • Suitable reaction media are solvents which are inert towards the reaction components.
  • solvents there may be mentioned the following: halogenated hydrocarbons such as methylene chloride, chloroform and carbontetrachloride; aliphatic and aromatic hydrocarbons such as petrol ether, cyclohexane, benzene, toluene and xylene; alcohols, like methanol and ethanol; ketones, like acetone, methylisobutylketone and isophorone; ethers, like diethylether, tetrahydrofuran and dioxane, and carboxylic acid nitriles, like acetonitrile.
  • organic bases such as triethylamine, N,N-dimethylaniline and pyridine bases, or inorganic bases, like oxides, hydroxides, and carbonates of the alkaline earth and alkali metals.
  • Liquid bases, like pyridine can also serve simultaneously as solvents.
  • the compounds of the invention which are made by the above processes can be isolated in conventional form, for instance by distilling off the solvent at atmospheric or reduced pressure, by precipitation with water or by fractional distillation.
  • Recyrstallization was effected from acetic acid ester/hexane.
  • the starting compound of this product is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid chloride.
  • 103.6 g (0.72 mol) were added batchwise to 280 ml of thionylchloride.
  • the mixture was then heated for 31/2 hours under reflux.
  • the excess thionylchloride was distilled off and the remaining residue was subjected to fractional distillation at a reduced pressure.
  • the compounds of the invention normally are colorless, non-smelling, crystalline materials or liquids which have a poor solubility in water, a moderate solubility in aliphatic hydrocarbons such as petrolether and cyclohexane, and are well soluble in halogenated hydrocarbons such as chloroform and carbontetrachloride; and aromatic hydrocarbons such as benzene, toluene, and xylene; ethers, such as diethylether, tetrahydrofuran and dioxane; carboxylic acid nitriles, such as acetonitrile; ketones, such as acetone; alcohols, such as methanol and ethanol; carboxylic acid amides, such as dimethylformamide and sulfoxides, such as dimethylsulfoxide.
  • solvents for the recrystallization there are preferred cyclohexane, acetonitrile and alcohol.
  • the 1,2,3-thiadiazole-5-carboxylic acid and their metal salts have a good water solubility but are only poorly soluble in organic solvents.
  • the starting products for making the compounds of the invention are conventional.
  • the compounds of the invention appearing from Table I below were emulsified or suspended in an amount of 5 kg of active agent per about 2.5 acres in 600 liter water per about 2.5 acres and were then applied by spraying in a hothouse in a preemergence and postemergence application to the following test plants which in the Table are indicated with the abbreviations listed as follows: Sinapis (Si), Solanum (So), Beta (Be), Gossypium (Go), Hordeum (Ho), Zea mays (Ze), Lolium (Lo) and Setaria (Se).
  • 1-2 growth regulating effects in the form of an intensive coloring of the primary leaves, retardation, stimulation of the budding or shoots, growth depression and diminution of the leaves, lower root development;
  • the plants listed below in Table II were treated in a postemergence application with the agents indicated in an amount of 1 kg of active agent per about 2.5 acres.
  • the treatment was effected in a hothouse.
  • the agent for this purpose was applied in a uniform manner to the soil as a suspension in 500 liter water per 2.5 acres.
  • Potted cotton plants in the stage of the incipient blossom buds were treated with the agent listed in Table 4 and at the dosage also indicated. The treatment was four times repeated. The amount of water to prepare the composition applied was 500 liters per about 2.5 acres.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Plural Heterocyclic Compounds (AREA)
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Abstract

1,2,3-thiadiazole-5-carboxylic acid derivatives having herbicidal and growth regulating activity and having the formula ##STR1## in which R1 is hydrogen or is alkyl of which the chain may be interrupted in one or several places by oxygen or sulfur or which may be substituted by halogen and in which
X is
(a) --Y--R2, wherein R2 is hydrogen, alkyl which may be substituted, aryl which may also be substituted, aryl-C1 -C2 -alkyl which may also be substituted, or a univalent metal equivalent and wherein Y is oxygen or sulfur, or
(b) wherein X constitutes the residue ##STR2## wherein R3 and R4 may be the same or different and have the meaning further defined in claim 1 of the accompanying specification.
The compounds are soil- or leaf-applicable herbicides with a high activity against seed weeds and resistant weeds.

Description

BACKGROUND OF THE INVENTION
The invention relates to 1,2,3-thiadiazole-5-carboxylic acid derivatives having a herbicidal and growth regulating activity and compositions containing the same.
Weed suppression in agricultural production has three essential functions: it must insure the growth of the crops it must assure the usefulness of the products harvested, and it must improve the working and production conditions. Effective weed suppression frequently constitutes the condition precedent to complete mechanization of a line of operation such as for instance grain, maize or beet planting, or form the basis for introducing new agricultural working methods and seeding processes, as for instance the direct speed process in case of maize, grain, soybean and cotton.
The prior art herbicides do not meet to the optimum degree the functions described, which functions have the highest significance for the progress of the agricultural and horticultural industry. There is therefore a substantial need for improving the technique of combating weeds.
An object of the present invention is therefore the provision of an agent which permits an improvement of the weed suppression techniques.
SUMMARY OF THE INVENTION
This problem is met by an agent which contains at least one compound of the formula ##STR3## in which
R1 is hydrogen or is alkyl of which the chain may be interrupted in one or several places by oxygen or sulfur and which may be substituted by halogen and in which
X constitutes (a) the residue --Y--R2 in which R2 is hydrogen, alkyl, which may be substituted, aryl, which may also be substituted, aryl-C1 -C2 -alkyl which may also be substituted, or constitutes a univalent metal equivalent and wherein
Y is oxygen or sulfur, or wherein
X constitutes (b) the residue ##STR4## in which R3 and R4 are the same or different and may be hydrogen, C1 -C18 alkyl which may also be substituted, C2 -C8 -alkenyl or alkinyl, aryl-C1 -C3 -alkyl which may also be substituted, a C3 -C8 -cycloaliphatic hydrocarbon residue which may also be substituted, C3 -C8 -cycloalkyl-C1 -C3 -alkyl- which may also be substituted, an aromatic hydrocarbon residue which may be substituted in one or several places by C1 -C6 -alkyl and/or halogen and/or C1 -C6 -alkoxy and/or nitro and/or trifluoromethyl or wherein R3 and R4 together with the adjoining nitrogen atom constitute a morpholino- piperidino- or pyrrolidino group.
The compounds of the invention are characterized by a soil- and/or leaf-herbicidal activity against seed weeds and resistant weeds. Their activity is partly systemic. They are particularly effective against dicotyl and monocotyl weed types of the families Digitalis, Trifolium, Portulaca, Papaver, Daucus, Kochia, Gypsophyla, Lactuca, Solanum, Escholtzia, Cheiranthus, Phacelia, Euphorbia, Linum, Convolvulus, Brassica, Datura, Cichorium, Ipomoea, Setaria, Agrostis, Phleum, Alopecurus, Phalaris, Dactylis, Festuca, Arrhenaterum, Lolium, Bromus, Avena, Allium, Cucumis, Medicago, Stellaria, Senecio, Matricaria, Lamium, Centaurea, Amaranthus, Galium, Chrysanthemum, Polygonum, Sorghum, Alopecurus, Echinochloa, Digitaria, Cyperus, Poa and others. The amounts employed are about 0.5 to 5 kg of active agent per about 2.5 acres.
A selective application is possible for instance in grain, cotton, soybean and plantation cultures. The highest activities are displayed by these agents, if they are sprayed onto a preexisting weed growth or are sprayed prior to the emergence. The so-called seed cultures can also be drilled a few days after spraying.
The individual compounds of the present invention may also modify the natural development of the plants so as to obtain various properties which may be agriculturally or horticulturally valuable.
The application of the compounds of the invention can be effected onto seeds or seedlings prior to or after emergence, onto roots, stems, leaves, blossoms, fruits or other plant parts.
The modification of the natural growth normally can be ascertained visually by changes of growth, of shape, of color or of structure of the treated plant or any of its parts.
The visually perceptible morphological modifications always presuppose a change of physiological and biochemical processes in the plant. The art has numerous analytical procedures to determine the kind and degree of such biochemical and physiological changes. Among these there may be mentioned the following changes of development of the plants as may be caused by the compounds of the invention:
Inhibition of the vertical growth
Inhibition of the root development
Stimulation of the budding and shoots
Intensifying of the formation of plant pigments
Defoliation.
The compounds of the invention, surprisingly, meet all functions necessary for an improvement of the weed suppression technique to an extent heretofore unknown.
Among the compounds of the invention the described effects are particularly obtained by those in which in the above formula I
R1 is hydrogen or C1 -C4 -alkyl which may be substituted by chlorine or bromine, for instance methyl, propyl, chloromethyl or bromomethyl,
R2 is hydrogen or C1 -C4 -alkyl, for instance methyl, ethyl, propyl, isopropyl, butyl, or is an aromatic hydrocarbon such as phenyl, 4-chlorophenyl, 4-nitrophenyl, 3-chlorophenyl, 2-chlorophenyl or 4-methylphenyl, or is an alkali metal atom, preferably lithium, sodium or potassium, or is a corresponding equivalent of a bivalent metal, for instance zinc, manganese, calcium, magnesium or barium, and wherein
Y is oxygen or sulfur and wherein if X is constituted by the residue ##STR5## R3 and R4 are the same or different and may be hydrogen, C1 -C8 alkyl which may be substituted by halogen, phenoxy, dialkylamino, alkoxy, alkoxycarbonyl, C2 -C6 alkenyl or alkinyl, C3 -C8 -cycloalkylmethyl which may also be substituted, C6 -C8 cycloalkyl which may also be substituted, or wherein R3 and R4 may be phenyl, chlorophenyl, nitrophenyl or methylphenyl.
More specifically, the residues identified as R3 and R4 may for instance be hydrogen, or in case of C1 -C18 alkyl may be methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, 2,2-dimethyl-1-propyl, n-heptyl, n-nonyl, n-undecyl, n-octadecyl, 3-methylbutyl, 4-methyl-2-pentyl, isobutyl, 3,3-dimethylbutyl, 2-butyl or 3,3-dimethyl-2-butyl, or in case of C1 -C18, alkyl may be 2-chloroethyl, 3-chloropropyl, 3-bromopropyl, 2-bromoethyl, 1-phenoxy-2-propyl, 3-dimethylaminopropyl, 2-dimethylaminoethyl, 3-diethylaminopropyl, tetrahydrofurfuryl, ethoxycarbonylmethyl, cyanomethyl, 2,2-methoxyethyl or 2-ethoxyethyl, or in case of C3 -C8 cycloalkyl-C1 -C3 -alkyl may be cyclohexylmethyl, 4-cyanocyclohexylmethyl, 4-hydroxymethylcyclohexylmethyl, 4-carbonylcyclohexylmethyl, cycloheptylmethyl or cyclooctylmethyl or cyclopropylmethyl, or in case of C2 -C8 -alkenyl or alkinyl may be 2-propenyl, 2-butenyl, 2-methyl-2-propenyl, 2-propinyl or 3-ethyl-1-pentine-3-yl, or in case of aryl-C1 -C3 -alkyl may be benzyl, 4-chlorobenzyl, 3-chlorobenzyl, 2-chlorobenzyl, 4-fluorobenzyl, 3-fluorobenzyl, 2-fluorobenzyl, 4-methylbenzyl, 3-methylbenzyl, 2-methylbenzyl, 3,4-methylenedioxybenzyl, 2,4-dichlorobenzyl, 3,4-dichlorobenzyl, 4-methoxybenzyl, 3-methoxybenzyl, 2-methoxybenzyl, 2-pyridylmethyl, 3-pyridylmethyl, 4-pyridylmethyl, α,α-dimethylbenzyl, 1-phenylethyl, 2-phenylethyl, 1,2-diphenylethyl, 2,2-diphenylethyl, 4-fluoro-α-methylbenzyl, 3-phenylpropyl or 2-furfuryl, or in case of a C3 -C8 -cycloaliphatic hydrocarbon residue may be cyclopropyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1-ethinylcyclohexyl, cycloheptyl or cyclooctyl, or in case of an aromatic hydrocarbon residue may be phenyl, 3-chlorophenyl, 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 4-fluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 1-naphthyl, 2-methoxyphenyl, 3-methoxyphenyl or 4-nitrophenyl.
The compounds of the invention can be used either individually, or in mixture with each other or in mixture with other agents.
Depending on the particular purpose of use there may for instance be added to the compounds of the invention the following herbicidal agents:
substituted anilines,
substituted aryloxycarboxylic acids and their salts, esters and amides,
substituted ethers,
substituted arsonic acids and their salts, esters and amides,
substituted benzimidazoles
substituted benzisothiazoles,
substituted benzthiadiazinone dioxides,
substituted benzoxazines,
substituted benzoxazinones,
substituted benzthiazoles,
substituted benzothiadiazines,
substituted biurets,
substituted quinolines,
substituted carbamates,
substituted aliphatic carboxylic acids and their salts, esters and amides,
substituted aromatic carboxylic acids and their salts, esters and amides,
substituted carbamoylalkyl-thio- or dithiophosphates
substituted quinazolines,
substituted cycloalkylamidocarbonylthiol acids and their salts, esters and amides,
substituted cycloalkylcarbonylamido-thiazoles,
substituted dicarboxylic acids and their salts, esters and amides,
substituted dihydrobenzofuranylsulfonates,
substituted disulfides,
substituted dipyridylium salts,
substituted dithiocarbamates,
substituted dithiophosphoric acids and their salts, esters and amides,
substituted urea derivatives,
substituted hexahydro-1H-carbothioates,
substituted hydantoines,
substituted hydrazides,
substituted hydrazonium salts,
substituted isoxazolpyrimidones,
substituted imidazoles,
substituted isothiazolpyrimidones,
substituted ketones,
substituted naphthoquinones,
substituted aliphatic nitriles,
substituted aromatic nitriles,
substituted oxadiazoles,
substituted oxadiazinons,
substituted oxadiazolidinedione,
substituted oxadiazinediones,
substituted phenols and their salts and esters,
substituted phosphonic acids and their salts, esters and amides,
substituted phosphoniumchlorides,
substituted phosphonalkylglycines,
substituted phosphites,
substituted phosphoric acids and their salts, esters and amides,
substituted piperidines,
substituted pyrazoles,
substituted pyrazolalkylcarboxylic acids and their salts, esters, and amides,
substituted pyrazolium salts,
substituted pyrazoliumalkylsulfates,
substituted pyridazines,
substituted pyridazones,
substituted pyridine-carboxylic acids and their salts, esters and amides,
substituted pyridines,
substituted pyridinecarboxylates,
substituted pyridinone,
substituted pyrimidone,
substituted pyrrolidine-carboxylic acids and their salts, esters and amides,
substituted pyrrolidines,
substituted pyrrolidones,
substituted arylsulfonic acids and their salts, esters and amides,
substituted styrenes,
substituted tetrahydro-oxadiazinediones,
substituted tetrahydromethanoindenes,
substituted tetrahydro-diazol-thiones,
substituted tetrahydro-thiadiazine-thiones,
substituted tetrahydro-thiadiazolediones,
substituted aromatic thiocarboxylic acid amides,
substituted thiocarboxylic acids and their salts, esters and amides,
substituted thiolcarbamates,
substituted thiourea derivatives,
substituted thiophosphoric acids and their salts, esters and amides,
substituted triazines,
substituted triazoles
substituted uracils, and
substituted urethidindiones,
auxin,
α-(2-chlorophenoxy)-propionic acid,
4-chlorophenoxyacetic acid
2,4-dichlorophenoxyacetic acid,
indolyl-3-acetic acid,
indolyl-3-butyric acid,
α-naphthyl acetic acid,
β-naphthoxy acetic acid,
naphthylacetamide,
n-m-tolylphthalamido acid,
gibberellins,
S,S,S-tri-n-butyl-triethiophosphoric acid ester,
cytoquinines,
2-chloroethylphosphoric acid,
2-chloro-9-hydroxyfluorene-9-carboxylic acid,
2-chloroethyl-trimethylammoniumchloride,
N,N-dimethylaminosuccinic acid amide,
2-isopropyl-4-trimethylammonio-5-methylphenylpiperidine-1-carboxylic acid esterchloride,
phenyl-isopropylcarbamate,
3-chlorophenyl-isopropylcarbamate,
ethyl-2-(3-chlorophenylcarbamoyloxy)-propionate,
maleic acid hydrazide,
2,3-dichloroisobutyric acid,
di-(methoxythiocarbonyl)disulfide,
1,1'-dimethyl-4,4'-bipyridylium-dichloride,
3,6-endoxohexahydrophthalic acid,
3-amino-1,2,4-triazole,
1,2,3-thiadiazolyl-5-yl-urea derivative,
1-(2-pyridyl)-3-(1,2,3-thiadiazole-5-yl)-urea
2-butylthio-benzthiazole,
2-(2-methylpropylthio)-benzthiazole,
3,4-dichloroisothiazole-5-carboxylic acid,
2,3-dihydro-5,6-dimethyl-1,4-dithiino-1,1,4,4-tetroxide,
arsenic acid,
cacodylic acid,
chlorates, preferably calcium chlorate, potassium chlorate, magnesium chlorate or sodium chlorate,
calcium cyanamide,
potassium iodide,
magnesium chloride,
abscisinic acid, nonanol,
N-(phosphonomethyl)-glycine-monoisopropyl-amine salt, and
N,N-bis-(phosphonomethyl)-glycine.
In addition there can also be used other additives for instance non-phytotoxic additives which in herbicides result in a synergistic increase of the activity and furthermore they can be used as wetting agents, emulsifiers, solvents and oily additives. The compounds of the invention or their mixture are preferably used in the form of compositions such as powders, dusting agents, granulates, solutions, emulsions or suspensions. There are added liquid and/or solid carrier materials or diluents and, if desired, wetting agents, adhesion promotion agents, emulsifiers and/or dispersing agents.
Suitable liquid carrier materials are, for instance, water, aliphatic and aromatic hydrocarbons, cyclohexanone, isophorone, dimethylsulfoxide, dimethylformamide, and furthermore mineral oil fractions.
As solid carrier materials there can be used mineral earths, for instance, tonsil, silicagel, talc, kaolin, attaclay, limestone, silicic acid, and plant products, for instance, flours.
There may also be added surface active agents, for instance calciumlignosulfonate, polyoxyethylene-alkylphenylether, naphthalenesulfonic acids and their salts, phenolsulfonic acid and their salts, formaldehyde condensation products, fatty alcohol sulfates, as well as substituted benzosulfonic acids and their salts.
The proportion of the active agent or agents can be varied in the different compositions within a broad range. The compositions may, for instance, contain about 10 to 80% by weight of active agents, 90 to 20% by weight of liquid or solid carrier materials and, if desired, up to 20% by weight of surface active agents in which case a corresponding reduction of the carrier materials is effected.
The application of the compounds of the invention and of the composition can be effected in conventional form, for instance with water as carrier materials in spray amounts of about 100 to 1000 liters to about 2.5 acres. The application of the agents is possible in the so-called "low-volume" and "ultra-low-volume" process as well as in the form of so-called microgranulates.
The new herbicides and growth regulating agents can be made in different ways.
(A) Compounds of the Formula ##STR6## may be reacted with thionylchloride, or
(B) 1,2,3-thiadiazole-5-carboxylic acid halides of the formula ##STR7## may be reacted with compounds of the formula
H--X                                                       IV
in the presence of acid acceptors, or in the following specific case
(C) 1,2,3-thiadiazole-5-carboxylic acid esters of the formula: ##STR8## are reacted with amines of the formula ##STR9##
In the above formulae R1, R2, R3, R4, X and Y have the same meaning as in the above formula I, Z is halogen, preferably chlorine, and R5 is C1 -C4 -alkoxy.
The reaction in all of these cases is carried out at a temperature between about 0° and 120° C. Preferred is a temperature between room temperature and the reflux temperature of the particular reaction mixture.
In order to effect the synthesis of the compounds of the invention the components are preferably used in about equimolar amounts. Suitable reaction media are solvents which are inert towards the reaction components. As such solvents there may be mentioned the following: halogenated hydrocarbons such as methylene chloride, chloroform and carbontetrachloride; aliphatic and aromatic hydrocarbons such as petrol ether, cyclohexane, benzene, toluene and xylene; alcohols, like methanol and ethanol; ketones, like acetone, methylisobutylketone and isophorone; ethers, like diethylether, tetrahydrofuran and dioxane, and carboxylic acid nitriles, like acetonitrile.
As acid acceptors there may be used organic bases such as triethylamine, N,N-dimethylaniline and pyridine bases, or inorganic bases, like oxides, hydroxides, and carbonates of the alkaline earth and alkali metals. Liquid bases, like pyridine can also serve simultaneously as solvents.
The compounds of the invention which are made by the above processes can be isolated in conventional form, for instance by distilling off the solvent at atmospheric or reduced pressure, by precipitation with water or by fractional distillation.
The following examples will further illustrate the making of the compounds of the invention.
EXAMPLE 1 4-Methyl-1,2,3-thiadiazole-5-carboxylic acid ethylester
(Compound No. 1) of the formula ##STR10##
432.5 g (2 mol) of 3-ethoxycarbonylhydrazonoacetic acid ethylester of a melting point between 59° and 61° C. were added batchwise to 700 ml thionylchloride at 20° C. while stirring the mixture and cooling it by ice. The solution was then permitted to stand for 20 hours at room temperature. The excess thionylchloride was then distilled off and the remaining residue was subjected to fractional distillation under reduced pressure. There were thus obtained 284.9 g (83% of the calculated value) of 4-methyl-1,2,3-thiadiazole-5-carboxylic acid ethylester as a colorless liquid having a boiling point of 66° to 69° C./0.5 torr.
EXAMPLE 2 4-methyl-1,2,3-thiadiazole-5-carboxylic acid
(Compound No. 2) of the formula ##STR11##
33.4 g (0.194 mol) of 4-methyl-1,2,3-thiadiazole-5-carboxylic acid ethylester were reacted with 80 ml of a 3 n methanol solution of sodium hydroxide and were permitted to stand for 16 hours at room temperature. The methanol was then withdrawn in a vacuum and the remaining sodium salt was washed with ether. The salt was subsequently dissolved in 200 ml water and acidified with dilute hydrochloric acid. It was then filtered off and subsequently washed with pentane.
Recyrstallization was effected from acetic acid ester/hexane.
The yield was 25.9 g=96% of the calculated value.
There were obtained colorless crystals of a melting point of 174° to 175° C.
EXAMPLE 3 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-fluorobenzylamide)
(Compound No. 3) of the formula ##STR12##
9.4 g (0.075 mol) of 4-fluorobenzylamine, dissolved in 100 ml of tetrahydrofuran were reacted at room temperature with 10.4 ml (0.075 mol) of triethylamine. A solution of 12.2 g (0.075 mol) of 4-methyl-1,2,3-thiadiazole-5-carboxylic acid chloride (b.p. 48° to 50° C./0.5 torr) dissolved in 50 ml tetrahydrofuran was then added dropwise at 10° C. upon stirring and cooling. Stirring was continued for 4 hours. After removing the precipitate by suction the filtrate was concentrated by evaporation and digested with ether.
Recrystallization was effected from ethanol.
The yield was 14.2 g=75.5% of the calculated value.
There were obtained colorless crystals of an m.p. of 106° to 107° C.
EXAMPLE 4 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(cyclohexylmethyl)-amide
(Compound No. 4) of the formula ##STR13##
17.2 g (0.1 mol) of 4-methyl-1,2,3-thiadiazole-5-carboxylic acid ethylester dissolved in 30 ml of absolute ethanol were reacted at room temperature with 11.3 g (0.1 mol) of aminomethylcyclohexane and subsequently heated under reflux for 3 hours. The solution was thereafter concentrated by evaporation and the remaining oil was digested with isopropylether.
Recrystallization was effected from cyclohexane.
The yield was 22.9 g=96% of the calculated value.
There were obtained colorless crystals, m.p. 79° to 80° C.
Making of the starting product for Compound No. 3
EXAMPLE 3
The starting compound of this product is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid chloride. In order to obtain this compound 103.6 g (0.72 mol) were added batchwise to 280 ml of thionylchloride. The mixture was then heated for 31/2 hours under reflux. The excess thionylchloride was distilled off and the remaining residue was subjected to fractional distillation at a reduced pressure. There were obtained 102 g (87.2% of the calculated value) of the above starting compound for Example 3 in the form of a colorless liquid; b.p. 48° to 50° C./0.5 torr.
In an analogous manner there were obtained the following compounds of the invention.
______________________________________                                    
Com-                                                                      
pound                       Physical                                      
No.   Name of Compound      Constants                                     
______________________________________                                    
5     4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-anilide                                           
                            m.p.: 116°-117° C.              
6     4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-chloro-                                        
      anilide)              m.p.: 106°-107° C.              
7     4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3-chloro-                                        
      anilide)              m.p.: 137°-138° C.              
8     4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3,4-dichloro-                                    
      anilide)              m.p.: 135°-136° C.              
9     4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid(4-chloro-                                         
      2-methylanilide)      m.p.: 142°-143° C.              
10    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-methyl-                                        
      anilide)              m.p.: 115°-116° C.              
11    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3-methyl-                                        
      anilide)              m.p.: 116°-117° C.              
12    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(4-methyl-                                        
      anilide)              m.p.: 118°-119° C.              
13    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3-trifluoro-                                     
      methylanilide)        m.p.: 123°-124° C.              
14    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(4-fluoro-                                        
      5-carboxylic acid-(4-fluoro-                                        
      anilide)              m.p.: 108°-109° C.              
15    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(4-nitro-                                         
      anilide)              m.p.: 179°-180° C.              
16    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(N-methyl-                                        
      anilide)              m.p.: 84°-85° C.                
17    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid dimethyl-                                         
      amide                 m.p.: 120°-125° C.              
18    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(N-benzyl-N-                                      
                            n.sub.D.sup. 20 : 1,5848                      
      2-propinylamide)                                                    
19    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(4-chloro-                                        
      anilide)              m.p.: 121°-122° C.              
20    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3,5-di-                                          
      chloroanilide)        m.p.: 195°-196° C.              
21    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid benzylamide                                       
                            m.p.: 63°-64° C.                
22    1,2,3-thiadiazole-5-carboxylic                                      
      acid ethylester       b.p.: 55°-57° C.                
23    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(4-chloro-                                        
      benzylamide)          m.p.: 109°-110° C.              
24    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-chloro-                                        
      6-methylanilide)      m.p.: 133°-134° C.              
25    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(N-cyano-                                         
      methyl-2,6-dimethylanilide)                                         
                            m.p.: 118°-119° C.              
26    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2,6-dimethyl-                                    
      anilide)              m.p.: 100°-101° C.              
27    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2,6-dichloro-                                    
      anilide)              m.p.: 116°-118° C.              
28    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid diethyl-                                          
      amide                 m.p. 111°-114° C.               
29    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-pyridyl-                                       
      methylamide)          m.p.: 75°-76° C.                
30    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3-pyridyl-                                       
      methylamide)          m.p.: 95°-96° C.                
31    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-chloro-                                        
      benzylamide)          m.p.: 68° C.                           
32    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3,4-methylene-                                   
      dioxybenzylamide)     m.p.: 87°-88° C.                
33    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid diisopropyl-                                      
      amide                 m.p.: 89°-91° C.                
34    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(N-benzyl-N-                                      
                            n.sub.D.sup.20 1,5838                         
      methylamide)                                                        
35    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2,4-dichloro-                                    
      benzylamide)          m.p.: 109°-111° C.              
36    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3,4-dichloro-                                    
      benzylamide)          m.p.: 109°-110° C.              
37    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3-chloro-                                        
      benzylamide)          m.p.: 64°-65° C.                
38    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-methoxy-                                       
      benzylamide)          m.p.: 96°-97° C.                
39    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3-methoxy-                                       
      benzylamide)          m.p.: 73°-75° C.                
40    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(4-methoxy-                                       
      benzylamide)          m.p.: 115°-117° C.              
41    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(4-methyl-                                        
      benzylamide)          m.p.: 115°-116° C.              
42    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-fluorobenzyl-                                  
      amide)                m.p.: 108°-109° C.              
43    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(N-ethyl-N-                                       
                            n.sub.D.sup.20 : 1,5751                       
      benzylamide)                                                        
44    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(N-benzyl-                                        
                            n.sub.D.sup.20 : 1,5695                       
      N-isopropylamide)                                                   
45    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(N-benzyl-N-                                      
                            n.sub.D.sup.20 : 1,5623                       
      butylamide)                                                         
46    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3-methyl-                                        
      benzylamide)          m.p.: 52°-53° C.                
47    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-naphthyl-                                      
      methylamide)          m.p.: 108°-109° C.              
48    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3,5-dimethyl-                                    
      benzylamide)          m.p.: 95°-96° C.                
49    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(4-tert-                                          
      butylbenzylamide)     m.p.: 65°-68° C.                
50    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid cyclohexyl-                                       
      amide                 m.p.: 101°-102° C.              
51    4-methyl-1,2,3-thiadiazole                                          
      5-carboxylic acid cycloctyl-                                        
      amide                 m.p.: 110°-111° C.              
52    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid cycloheptyl-                                      
      amide                 m.p.: 110°-112  C.                     
53    4-methyl-1,2,3-thiadiazole                                          
      5-carboxylic acid cyclopentyl-                                      
      amide                 m.p.: 87°-89° C.                
54    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid cyclopropyl-                                      
      amide                 m.p.: 89°-91° C.                
55    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid butylamide                                        
                            n.sub.D.sup.20 : 1,5302                       
56    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-methyl-                                        
                            n.sub.D.sup.20 : 1,5267                       
      propylamide)                                                        
57    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(1,1-dimethyl-                                    
      ethylamide)           m.p.: 88°-90° C.                
58    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-propenyl-                                      
      amide                 m.p.: 58°-59° C.                
59    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(ethoxy-                                          
                            n.sub.D.sup.20 : 1,5298                       
      carbonylmethylamide                                                 
60    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-ethoxy-                                        
                            n.sub.D.sup.20 : 1,5258                       
      ethylamide)                                                         
61    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(1,1-diethyl-                                     
      2-propinylamide)      m.p.: 74°-75° C.                
62    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2,2-diethoxy-                                    
                            n.sub.D.sup.20 : 1,5089                       
      ethylamide)                                                         
63    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3-dimethyl-                                      
                            n.sub.D.sup.20 : 1,5290                       
      aminopropylamide)                                                   
64    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(diphenyl-                                        
      amide)                m.p.: 116°-119° C.              
65    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(1-ethinyl-                                       
      cyclohexylamide)      m.p.: 91°-93° C.                
66    (4-methyl-1,2,3-thiadiazole-                                        
      5-yl)-pyrrolidinoketone                                             
                            n.sub.D.sup.20 : 1,5618                       
67    (4-methyl-1,2,3-thiadiazole-                                        
      5-yl)-piperidinoketone                                              
                            n.sub.D.sup.20 : 1,5550                       
68    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-furfuryl)-                                     
      amide                 m.p.: 49°-50° C.                
69    (4-methyl-1,2,3-thiadiazole-                                        
      5-yl)-morpholinoketone                                              
                            m.p.: 85°-86° C.                
70    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(1,-phenyl-                                       
      ethyl)-amide          m.p.: 78°-79° C.                
71    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-cyclopropyl-                                      
                            n.sub.D.sup.20 : 1,5470                       
      methylamide                                                         
72    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-morpholino-                                       
      amide                 m.p.: 184°-185° C.              
73    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-piperidino-                                       
      amide                 m.p.: 155°-156° C.              
74    4-methyl-1,2,4-thiadiazole-                                         
      5-carboxylic acid-(N-benzyl-                                        
      anilide)              m.p.: 83°-84° C.                
75    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-propylamide                                       
                            n.sub.D.sup.20 : 1,5360                       
76    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-isopropyl-                                        
      amide                 m.p.: 72°-73° C.                
77    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-cyclohexyl-                                       
                            n.sub.D.sup.20 : 1,5176                       
      methylester                                                         
78    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(4-chlorobenzyl)-                                 
      ester                 m.p.: 89°-90° C.                
79    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-benzylester                                       
                            n.sub.D.sup.20 : 1,5649                       
80    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid amide                                             
                            m.p.: 122°-124°  C.             
81    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-methyl-                                        
      cyclohexylamide)      m.p.: 78°-79°0 C.               
82    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3-methyl-                                        
      cyclohexylamide)      m.p.: 90°-92° C.                
83    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(4-methyl-                                        
      cyclohexylamide)      m.p.: 118°-120° C.              
84    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(tetrahydro-                                      
                            n.sub.D.sup.20 : 1,5471                       
      furfurylamide)                                                      
85    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(cycloheptyl-                                     
                            n.sub.D.sup.20 : 1,5476                       
      methylamide)                                                        
86    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(cyclooctyl-                                      
                            n.sub.D.sup.20 : 1,5439                       
      methylamide)                                                        
87    4-propyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(cyclohexyl-                                      
      methylamide)          m.p.: 51°-52° C.                
88    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(1,2,3-tri-                                       
      methylpropylamide)    m.p.: 95°-96° C.                
89    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3-phenyl-                                        
                            n.sub.D.sup.20 : 1,5790                       
      propylamide)                                                        
90    4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-phenyl-                                        
                            n.sub.D.sup.20 : 1,5838                       
      ethylamide)                                                         
91    4-ethyl-1,2,3-thiadiazole-                                          
      5-carboxylic acid-(cyclohexyl-                                      
                            n.sub.D.sup.20 : 1,5352                       
      methylamide)                                                        
92    4-ethyl-1,2,3-thiadiazole-5-                                        
      carboxylic acid ethyl ester                                         
                            b.p.: 74-75/                                  
                            0.1 torr                                      
93    4-propyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid       m.p.: 101°-103° C.              
94    4-methyl-1,2,3-thiadiazole-                                         
      carboxylic acid-(1,2-diphenyl-                                      
      ethyl)-amide          m.p.: 158° C.                          
95    4-methyl-1,2,3-thiadiazole 5-                                       
      carboxylic acid-N-(2-cyanoethyl)-                                   
      benzyl]amide          m.p.: 81° C.                           
96    4-methyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-[1-4-fluoro-                                        
      phenyl)-ethyl]-amide  m.p.: 112° C.                          
97    4-methyl-1,2,3-thiadiazole-                                         
      carboxylic acid-(N-methyl-                                          
                            n.sub.D.sup.20 : 1,5414                       
      cyclohexylmethyl)-amide                                             
98    4-propyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-(4-methylbenzyl-                                    
      amide                 m.p.: 78° C.                           
99    4-propyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-(4-chlorobenzyl-                                    
      amide                 m.p.: 102°-103° C.              
100   4-propyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-(4-fluorobenzyl)-                                   
      amide                 m.p.: 77°-78° C.                
101   4-propyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-(3,4-dichloro-                                      
      benzyl)-amide         m.p.: 97°-98° C.                
102   4-propyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-cyclohexylamide                                     
                            m.p. 74°-75° C.                 
103   4-propyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-(2-methylcyclo-                                     
      hexylamide)           m.p.: 85° C.                           
104   4-propyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-(3-methylcyclo-                                     
      hexylamide)           m.p.: 70° C.                           
105   4-propyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-(4-methylcyclo-                                     
                            n.sub.D.sup.20 : 1,5319                       
      hexylamide)                                                         
106   4-propyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-(cycloheptyl-                                       
      methyl)-amide         m.p.: 40°-42° C.                
107   4-propyl-1,2,3-thiadiazole-                                         
      carboxylic acid-(cyclooctyl-                                        
                            n.sub.D.sup.20 : 1,5323                       
      methyl)-amide                                                       
108   4-methyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-(3-hydroxy-                                         
      anilide)              m.p. 176°-177° C.               
109   4-methyl-1,2,3-thiadiazole-                                         
      carboxylic acid-(4-chloro-                                          
      phenyl-ester          m.p.: 71°-74° C.                
110   1,2,3-thiadiazole-5-carboxylic                                      
      acid-(cyclohexylmethyl)-amide                                       
                            m.p.: 115°-116° C.              
111   4-methyl1,2,3-thiadiazole-5-                                        
      carboxylic acid-(3,4-dichloro-                                      
      phenylester)          m.p.: 66°-68° C.                
112   4-methyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid phenylester                                         
                            n.sub.D.sup.20  : 1,5695                      
113   4-methyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-(1,2-dimethyl-                                      
                            n.sub.D.sup.20 : 1,5159                       
      butyl)-amide                                                        
114   4-methyl-1,2,3-thiadiazole-5-                                       
      carboxylic acid-(3-methylbutyl)-                                    
                            n.sub.D.sup.20 : 1,5243                       
      amide                                                               
115   4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(1-hydroxy-                                       
      cyclohexylmethyl)-amide                                             
                            m.p.: 74°-75° C.                
116   4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(2-dimethyl-                                      
                            n.sub.D.sup.20 : 1,5360                       
      aminoethyl)-amide                                                   
117   4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3,3-di-                                          
      methylbutyl)-amide    m.p. 50°-52° C.                 
118   4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3-phenox-                                        
                            n.sub.D.sup.20 : 1,5989                       
      benzyl)-ester                                                       
119   4-methyl-1,2,3-thiadiazole-                                         
      5-carboxylic acid-(3-methyl-                                        
      carbamoyloxy-anilide) m.p.: 173° C.                          
                            (decomposed)                                  
______________________________________
The compounds of the invention normally are colorless, non-smelling, crystalline materials or liquids which have a poor solubility in water, a moderate solubility in aliphatic hydrocarbons such as petrolether and cyclohexane, and are well soluble in halogenated hydrocarbons such as chloroform and carbontetrachloride; and aromatic hydrocarbons such as benzene, toluene, and xylene; ethers, such as diethylether, tetrahydrofuran and dioxane; carboxylic acid nitriles, such as acetonitrile; ketones, such as acetone; alcohols, such as methanol and ethanol; carboxylic acid amides, such as dimethylformamide and sulfoxides, such as dimethylsulfoxide.
As solvents for the recrystallization there are preferred cyclohexane, acetonitrile and alcohol. The 1,2,3-thiadiazole-5-carboxylic acid and their metal salts have a good water solubility but are only poorly soluble in organic solvents.
The starting products for making the compounds of the invention are conventional.
The following examples will further illustrate the applications and uses of the compounds of the invention.
APPLICATIONS AND USES EXAMPLE 5
The compounds of the invention appearing from Table I below were emulsified or suspended in an amount of 5 kg of active agent per about 2.5 acres in 600 liter water per about 2.5 acres and were then applied by spraying in a hothouse in a preemergence and postemergence application to the following test plants which in the Table are indicated with the abbreviations listed as follows: Sinapis (Si), Solanum (So), Beta (Be), Gossypium (Go), Hordeum (Ho), Zea mays (Ze), Lolium (Lo) and Setaria (Se).
Three weeks after treatment the results were evaluated on the following scale:
0=no effect
1-2=growth regulating effects in the form of an intensive coloring of the primary leaves, retardation, stimulation of the budding or shoots, growth depression and diminution of the leaves, lower root development;
3-4=plants no longer viable, or withered away.
The letter V in the following Table indicates preemergence application and the letter N indicates postemergence application.
                                  TABLE I                                 
__________________________________________________________________________
                   Si  So  Be  Go  Ho  Ze  Lo  Se                         
Compound of the invention                                                 
                   V N V N V N V N V N V N V N V N                        
__________________________________________________________________________
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid    0 3 0 4 1 3 0 0 0 3 0 3 1 1 0 3                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid anilide                                                   
                   0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(2-chloroanilide)                                         
                   0 3 1 3 0 3 0 0 0 1 0 0 2 3 0 3                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(3-chloroanilide)                                         
                   0 4 0 3 0 4 0 1 0 2 0 0 0 2 0 3                        
4-methyl-1,2,3-thiadiazole-                                               
5-carboxylic acid-(3-methyl-                                              
anilide)           0 4 0 4 0 4 0 0 0 0 0 2 1 1 3 3                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(4-methyl-anilide                                         
                   0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 1                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(4-fluoro-anilide)                                        
                   0 4 0 2 0 4 0 0 0 0 0 0 1 2 0 3                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(3-trifluoro-                                             
methylanilide)     0 3 0 0 0 3 0 0 0 0 0 0 1 0 0 3                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(N-benzyl-N-                                              
2-propinylamide)   1 0 0 2 0 3 0 0 0 3 0 0 0 0 0 4                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(4-chloroanilide)                                         
                   0 0 0 0 0 1 0 0 0 1 0 1 0 0 0 1                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(3,5-dichloro-                                            
anilide)                                                                  
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid benzylamide                                               
                   1 4 2 3 3 3 1 3 3 3 1 3 3 3 3 4                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(4-chloro-                                                
benzylamide)       4 4 4 3 4 4 2 3 4 3 2 2 4 3 4 4                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(2-chloro-6-                                              
methylanilide)     3 2 3 2 0 0 0 0 0 0 0 0 0 0 2 3                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(2,6-dichloro-                                            
anilide)           1 4 2 3 0 2 0 1 1 1 0 0 0 1 2 2                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid diethylamide                                              
                   0 0 0 1 0 0 0 1 0 0 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(2-pyridyl-                                               
methylamide)       0 1 0 1 1 0 0 1 0 0 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(2-chloro-benzyl-                                         
amide)             2 2 3 2 2 1 0 1 2 0 0 0 4 1 3 1                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(cyclohexyl-                                              
methyl)-amide      4 4 4 4 4 4 4 4 4 2 4 2 4 4 4 4                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(3,4-methylene-                                           
dioxybenzylamide)  2 2 1 0 0 0 0 1 1 1 0 0 1 1 1 1                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(2,4-dichloro-                                            
benzylamide)       0 3 0 0 0 2 0 0 0 0 0 0 1 1 0 4                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(3,4-dichloro-                                            
benzylamide)       0 1 0 0 0 1 0 1 0 0 0 1 0 0 0 1                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(3-chloro-                                                
benzylamide)       0 1 0 0 0 1 0 1 0 1 0 1 0 0 0 1                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(2-methoxy-                                               
benzylamide)       0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(4-fluoro-                                                
benzylamide)       4 4 4 4 4 4 3 4 4 2 3 1 4 4 4 4                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(4-methyl-                                                
benzylamide)       3 1 3 3 1 0 1 2 2 0 0 0 3 1 3 2                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(2-fluoro-                                                
benzylamide)       4 4 4 4 4 4 4 4 4 4 2 0 4 4 4 4                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-cyclohexylamide                                           
                   4 4 4 3 4 4 3 3 3 3 3 2 4 4 4 4                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-cyclohexylamide                                           
                   2 4 4 3 2 4 2 3 3 2 2 2 3 2 1 3                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-cycloheptylamide                                          
                   4 4 4 3 4 4 2 3 3 2 2 0 3 2 2 1                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-cyclopentylamide                                          
                   1 2 1 0 0 1 0 0 0 0 0 0 1 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-cyclopropylamide                                          
                   1 1 1 0 0 1 0 0 0 1 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid butylamide                                                
                   3 3 2 1 4 3 2 3 1 1 0 0 1 1 3 2                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(2-furfuryl)-amide                                           
                   0 0 0 0 0 1 0 0 0 1 0 0 0 0 0 1                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(1-phenylethyl)-amide                                        
                   0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-cyclopropylmethylamide                                       
                   0 1 0 0 0 3 0 1 0 0 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-morpholino-amide                                             
                   0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-piperidino-1mide                                             
                   0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(N-benzylanilide)                                            
                   0 0 0 0 0 1 0 0 0 3 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-propylamide                                                  
                   0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-isopropylamide                                               
                   0 0 0 0 0 0 0 1 0 1 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-cyclohexylmethylester                                        
                   0 0 0 3 0 1 0 1 0 1 0 0 0 1 0 0                        
4-methyl-1,2,3-thiadiazole-5-yl)-                                         
morpholinoketone   0 0 0 0 0 1 0 0 0 1 0 1 0 0 0 1                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(4-chlorobenzyl)-ester                                       
                   0 2 0 3 0 3 0 2 0 1 0 0 0 1 0 1                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-benzylester                                                  
                   0 1 0 3 0 2 0 2 0 2 0 0 0 1 0 1                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid amide 0 1 0 1 0 0 0 0 0 0 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(2-methylcyclohexylamide)                                    
                   4 4 4 4 4 4 0 0 4 2 2 0 4 4 4 4                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(3-methylcyclohexyl-                                         
amide)             4 4 4 4 4 4 0 0 4 4 4 4 4 4 4 4                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(4-methylcyclohexyl-                                         
amide)             2 2 4 2 2 0 0 0 2 0 0 0 2 2 2 4                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(tetrahydrofurfuryl-                                         
amide)             4 4 2 2 3 2 0 0 0 0 0 0 3 2 2 1                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(cycloheptylmethylamide)                                     
                   4 4 4 4 4 4 0 0 4 4 4 4 4 4 4 4                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(cyclooctylmethylamide)                                      
                   4 4 4 4 4 4 0 0 4 4 4 4 4 4 4 4                        
4-propyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(cyclohexylmethylamide)                                      
                   0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(1,2,2-trimethylpropyl-                                      
amide)             0 2 0 2 0 0 0 0 0 0 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-car-                                         
boxylic acid-(2-phenylethylamide)                                         
                   0 2 0 2 0 2 0 0 0 0 0 0 0 2 0 0                        
4-ethyl-1,2,3-thiadiazole-5-car-                                          
boxylic acid-(cyclohexylmethylamide)                                      
                   3 4 4 3 4 4 0 2 0 0 0 0 0 2 0 2                        
4-ethyl-1,2,3-thiadiazole-5-                                              
carboxylic acid ethylester                                                
                   0 0 0 0 1 1 0 0 0 0 0 0 0 0 0 0                        
4-propyl-1,2,3-thiadiazole-5-                                             
carboxylic acid    0 0 3 3 0 0 0 0 0 0 0 0 0 0 0 0                        
4-propyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(4-methyl-                                                
benzyl)-amide      1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0                        
4-propyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(4-chloro-                                                
benzyl)-amide      1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0                        
4-propyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(4-fluoro-                                                
benzyl)-amide      1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0                        
4-propyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(3,4-dichloro-                                            
benzyl)-amide      1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0                        
4-propyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-cyclohexylamide                                           
                   1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0                        
4-propyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(2-methylcyclo-                                           
                   1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0                        
hexylamide)                                                               
4-propyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(3-methylcyclo-                                           
                   1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0                        
hexylamide)                                                               
4-propyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(4-methylcyclo-                                           
                   1 1 0 0 1 1 0 0 0 0 0 0 0 0 0 0                        
hexylamide)                                                               
4-propyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(cyclooctyl-                                              
                   3 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0                        
methyl)-amide                                                             
4-propyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(cycloheptyl-                                             
                   3 3 1 1 0 0 0 0 0 0 0 0 0 0 0 0                        
methyl)-amide                                                             
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(1,2-diphenyl-                                            
ethyl)-amide       0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 2                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-[N-(2-cyanoethyl)-                                        
                   1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0                        
benzyl]-amide                                                             
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-[1-(4-fluoro-                                             
                   4 4 0 0 0 0 0 0 1 1 0 0 0 0 4 4                        
phenyl)-ethyl]-amide                                                      
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(N-methyl-cyclo-                                          
                   4 4 4 4 4 4 0 2 0 0 0 0 0 0 0 2                        
hexylmethyl)-amide                                                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(3-hydroxyanilide)                                        
                   1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(1-hydroxy-cyclo-                                         
                   4 4 4 4 4 4 4 4 4 3 4 3 4 3 4 3                        
hexylmethyl)-amide                                                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid phenylester                                               
                   --                                                     
                     2 --                                                 
                         2 --                                             
                             1 --                                         
                                 1 --                                     
                                     1 --                                 
                                         1 --                             
                                             1 --                         
                                                 2                        
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(1,3-dimethyl-                                            
                   --                                                     
                     3 --                                                 
                         2 --                                             
                             2 --                                         
                                 3 --                                     
                                     3 --                                 
                                         0 --                             
                                             0 --                         
                                                 3                        
butyl)-amide                                                              
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(3-methylbutyl)-                                          
                   4 4 4 4 4 4 4 4 3 2 3 2 4 1 4 4                        
amide                                                                     
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(2-dimethyl-                                              
                     --                                                   
                       --                                                 
                         --                                               
                           --                                             
                             --                                           
                               --                                         
                                 --                                       
                                   --                                     
                                     --                                   
                                       --                                 
                                         --                               
                                           --                             
                                             --                           
                                               --                         
                                                 --                       
aminoethyl)-amide                                                         
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(3-phenoxy-                                               
                     1 --                                                 
                         1 --                                             
                             --                                           
                               --                                         
                                 --                                       
                                   --                                     
                                     --                                   
                                       --                                 
                                         --                               
                                           --                             
                                             --                           
                                               --                         
                                                 --                       
benzyl)-ester                                                             
4-methyl-1,2,3-thiadiazole-5-                                             
                     --                                                   
                       --                                                 
                         --                                               
                           --                                             
                             --                                           
                               --                                         
                                 --                                       
                                   --                                     
                                     --                                   
                                       --                                 
                                         --                               
                                           --                             
                                             --                           
                                               --                         
                                                 --                       
carboxylic acid-(3-methylcar-                                             
bamoyloxy-anilide)                                                        
4-methyl-1,2,3-thiadiazole-5-                                             
                     4 4 4 4 4 4 3 3 2 1 1 4 1 4 2                        
carboxylic acid-(3,3-dimethyl-                                            
butyl)-amide                                                              
__________________________________________________________________________
Analogous activity have the following compounds:
4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(N-ethyl-N-benzylamide).
4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(N-benzyl-N-isopropylamide).
4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(N-benzyl-N-butylamide).
4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3-methylbenzylamide).
4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2-naphthylmethyl)-amide.
4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3,5-dimethylbenzyl)-amide.
4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-tert-butylbenzyl)-amide.
EXAMPLE 6
The plants listed below in Table II were treated in a postemergence application with the agents indicated in an amount of 1 kg of active agent per about 2.5 acres. The treatment was effected in a hothouse. The agent for this purpose was applied in a uniform manner to the soil as a suspension in 500 liter water per 2.5 acres.
The results show that the compounds of the invention destroyed a large selection of plant species while the important cultures of maize and cotton were not damaged.
The evaluation was on a scale from 0=total destruction to 10=no injury to plant.
                                  TABLE II                                
__________________________________________________________________________
                                                    Chry-                 
                                             Ama-   san-   Poly-          
                       cot-                                               
                          Stel-                                           
                              Se- Matri-                                  
                                      Lam-                                
                                         Cent-                            
                                             ran-                         
                                                 Gal-                     
                                                    the-                  
                                                        Ipo-              
                                                           go-            
Compounds of the invention                                                
                   maize                                                  
                       ton                                                
                          laria                                           
                              necio                                       
                                  caria                                   
                                      ium                                 
                                         aurea                            
                                             thus                         
                                                 ium                      
                                                    mum moea              
                                                           num            
__________________________________________________________________________
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(cyclohexyl-                                              
methyl)-amide      10  10 0   0   0   0  0   0   0  0   0  0              
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(4-fluorobenzyl-                                          
amide)             10  10 0   0   0   0  0   0   0  0   0  0              
Untreated          10  10 10  10  10  10 10  10  10 10  10 10             
__________________________________________________________________________
                      Alo-         Dig-                 Es-               
                   Av-                                                    
                      pecu-                                               
                          Echino-                                         
                               Set-                                       
                                   it-                                    
                                      Cy- Sor-   Sol-                     
                                                     Dat-                 
                                                        cholt-            
                                                            Ko-           
Compounds of the invention                                                
                   ena                                                    
                      rus chloa                                           
                               aria                                       
                                   aria                                   
                                      perus                               
                                          ghum                            
                                              Poa                         
                                                 anum                     
                                                     ura                  
                                                        zia chia          
__________________________________________________________________________
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(cyclohexyl-                                              
methyl)-amide      0  0   0    0   0  0   0   0  0   0  0   0             
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(4-fluorobenzyl-                                          
amide)             0  0   0    0   0  7   0   0  0   0  0   0             
Untreated          10 10  10   10  10 10  10  10 10  10 10  10            
__________________________________________________________________________
EXAMPLE 7
4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(cyclohexylmethyl)-amide and 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-fluorobenzylamide)emulsified in 500 liters of water per 2.5 acres were applied in a hothouse in amounts of 1 kg of active agent per 2.5 acres to the following plants: Stellaria, Senecio, Matricaria, Lamium, Centaurea, Amaranthus, Galium, Chrysanthemum, Ipomoea, Polygonum, Brassica, Solanum, Allium, Pisum, Portulaca, Kochia, Daucus, Cheiranthus, Euphorbia, Datura and Cichorium.
All plants listed were destroyed. Two days later cultures of maize, cotton and soybean were seeded into the treated soil. The cultures remained without damage and could grow free of competitive weeds.
EXAMPLE 8
4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(cyclohexylmethyl)-amide in an amount of 1 kg per 2.5 acres was sprayed in a hothouse in the form of an emulsion with 500 liter of water per 2.5 acres onto the plants listed below in Table 3.
The results show that the agricultural plants rice and maize remained without damage while important weed type grasses were destroyed.
The evaluation was on a scale wherein 0=total destruction and 10=no damage to the plants.
                                  TABLE III                               
__________________________________________________________________________
                                    Dig-                                  
                                       Alo-                               
                            Echino-                                       
                                 Se-                                      
                                    it-                                   
                                       pecu-                              
Compound of the invention                                                 
              grain                                                       
                 wheat                                                    
                     maize                                                
                         rice                                             
                            chloa                                         
                                 taria                                    
                                    aria                                  
                                       rus                                
__________________________________________________________________________
4-methyl-1,2,3-thiadiazole-                                               
5-carboxylic acid-(cyclo-                                                 
hexylmethyl)-amide                                                        
              10 10  10  10 0    0  0  0                                  
4-methyl-1,2,3-thiadiazole-                                               
5-carboxylic acid-(4-fluoro-                                              
benzylamide)  10 10  10  10 0    0  0  2                                  
untreated     10 10  10  10 10   10 10 10                                 
__________________________________________________________________________
EXAMPLE 9
Potted cotton plants in the stage of the incipient blossom buds were treated with the agent listed in Table 4 and at the dosage also indicated. The treatment was four times repeated. The amount of water to prepare the composition applied was 500 liters per about 2.5 acres.
After a few days the percentage of dropped leaves was determined as proof of the defoliation. The following table shows the superiority of the compound of the invention.
              TABLE IV                                                    
______________________________________                                    
                   active agent                                           
                   kg/about    defolia-                                   
Compound of the invention                                                 
                   2.5 acres   tion                                       
______________________________________                                    
4-methyl-1,2,3-thiadiazole-5-                                             
carboxylic acid-(cyclohexyl-                                              
methyl)-amide      0.05        68.8                                       
comparison compound                                                       
(U.S. Pat. No. 2,954,407)                                                 
tri-n-butyl-trithiophosphate                                              
                   0.05        10.0                                       
                   0.50        53.3                                       
______________________________________
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention.

Claims (66)

What is claimed as new and desired to be protected by Letters Patent is set forth in the appended claims:
1. A comound of the formula ##STR14## wherein R1 is hydrogen, C1 -C4 alkyl, chloromethyl, or bromomethyl; and
X has the formula ##STR15## where R3 and R4 are the same or different and are hydrogen, C1 -C18 alkyl, mono- or disubstituted C1 -C18 alkyl substituted in the 1-, 2- or 3-position by halogen, C1 -C6 alkoxy, phenoxy, dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl or cyano, tetrahydrofurfuryl, C3 -C8 cycloalkylmethyl, C2 -C8 2- or 3-alkenyl or alkinyl, phenyl or diphenyl C1 -C3 alkyl, mono- or disubstituted benzyl substituted by one or more of halogen, methylenedioxy, C1 -C6 alkyl, C1 -C6 alkoxy, trifluoromethyl or nitro, α-methyl- or α,α-dimethylbenzyl, pyridyl, furfuryl, C3 -C8 cycloalkyl, C1 -C6 alkyl or ethinyl substituted C3 -C8 cycloalkyl, phenyl, mono- or disubstituted phenyl substituted by one or more of halogen, methylenedioxy, C1 -C6 alkyl, C1 -C6 alkoxy, trifluoromethyl or nitro, or naphthyl, or R3 and R4 together with the adjoining nitrogen atom constitute a morpholine, piperidine or pyrrolidine group.
2. A herbicidal and growth regulating composition for plants comprising about 10 to 80% by weight of the active agent defined in claim 1 and about 90 to 20% by weight of liquid or solid carrier materials in which composition part of the carrier materials may be replaced by up to 20% by weight of surface active agents.
3. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-fluorobenzylamide).
4. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(cyclohexylmethyl)-amide.
5. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-anilide.
6. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2-chloro-anilide).
7. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3-chloroanilide).
8. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3,4-dichloroanilide).
9. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-chloro-2-methylanilide).
10. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2-methylanilide).
11. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3-methylanilide).
12. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-methylanilide).
13. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-fluoroanilide).
14. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3-trifluoromethylanilide).
15. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-nitroanilide).
16. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(N-methylanilide).
17. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-dimethylamide.
18. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(N-benzyl-N-2-propinylamide).
19. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-chloroanilide).
20. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3,5-dichloroanilide).
21. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-benzylamide.
22. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-chlorobenzylamide).
23. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2-chloro-6-methylanilide).
24. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(N-cyanmethyl-2,6-dimethylanilide).
25. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2,6-dimethylanilide).
26. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2,6-dichloroanilide).
27. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-diethylamide.
28. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2-pyridylmethylamide).
29. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3-pyridylmethylamide).
30. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2-chlorobenzylamide).
31. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3,4-methylendioxybenzylamide).
32. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-diisopropylamide.
33. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(N-benzyl-N-methylamide).
34. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2,4-dichlorobenzylamide).
35. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3,4-dichlorobenzylamide).
36. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3-chlorobenzylamide).
37. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2-methoxybenzylamide).
38. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3-methoxybenzylamide).
39. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-methoxybenzylamide).
40. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-methylbenzylamide).
41. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2-fluorobenzylamide).
42. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(N-ethyl-N-benzylamide).
43. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(N-benzyl-N-isopropylamide).
44. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(N-benzyl-N-butylamide).
45. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3-methylbenzylamide).
46. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2-naphthylmethylamide).
47. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3,5-dimethylbenzylamide).
48. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(4-tert-butylbenzylamide).
49. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-cyclohexylamide.
50. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-cyclooctylamide.
51. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-cycloheptylamide.
52. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-cyclopentylamide.
53. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-cyclopropylamide.
54. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-butylamide.
55. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2-methylpropylamide).
56. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(1,1-dimethylethylamide).
57. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2-propenylamide).
58. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(ethoxycarbonylmethylamide).
59. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2-ethoxyethylamide).
60. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(1,1-diethyl-2-propinylamide)
61. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(2,2-diethoxyethylamide).
62. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(3-dimethylaminopropylamide).
63. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(diphenylamide).
64. The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(1-ethinylcyclohexylamide).
65. The compound of claim 1 which is (4-methyl-1,2,3-thiadiazole-5-yl)-pyrrolidinoketone.
66. The compound of claim 1 which is (4-methyl-1,2,3-thiadiazole-5-yl)-piperidinoketone.
US05/918,462 1977-06-23 1978-06-23 1,2,3-Thiadiazole-5-carboxylic acid derivatives, herbicidal and growth regulating compositions containing the same and process for making same Expired - Lifetime US4177054A (en)

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Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4314839A (en) * 1979-04-05 1982-02-09 Schering Aktiengesellschaft 1,2,3-Thiadiazole-5-carboxylic acid amide derivatives, process for making the same and herbicidal growth regulating defoliating and fungicidal compositions containing same
US4341551A (en) * 1979-03-12 1982-07-27 Schering Ag 1,2,3,-Thiadiazole-5-carboxylic acid derivatives
US4359471A (en) * 1980-11-08 1982-11-16 Basf Aktiengesellschaft 2-(N-Aryl,N-1,2,3-thiadiazolylcarbonyl)-aminobutyro-lactones, their preparation, fungicidal agents containing these compounds, and their use as fungicides
US4410538A (en) * 1980-08-14 1983-10-18 Basf Aktiengesellschaft N-Disubstituted aniline derivatives, their preparation, their use as microbicides and agents for such use
US4902804A (en) * 1985-10-03 1990-02-20 Pennwalt Corporation Multifunctional thiadiazole lubricant additives
EP0347377A3 (en) * 1988-06-13 1990-04-04 Ciba-Geigy Ag 1,2,3-benzothiadiazole-4-carboxylic-acid derivatives as plant growth regulators
EP0313512A3 (en) * 1987-08-21 1990-04-04 Ciba-Geigy Ag Benzothiadiazoles and their use in processes and compositions against plant diseases
US4990652A (en) * 1985-10-03 1991-02-05 Atochem North America, Inc. Intermediates for preparing multifunctional thiadiazole lubricant additives
US5098918A (en) * 1985-05-17 1992-03-24 The Upjohn Company 1,2,3-thiadiazole compounds, compositions and method of anti-thrombotic treatment
WO1996029871A3 (en) * 1995-03-31 1996-11-14 Nihon Nohyaku Co Ltd An agricultural and horticultural disease controller and a method for controlling the diseases
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US6166054A (en) * 1995-03-31 2000-12-26 Nihon Nohyaku Co., Ltd. Agricultural and horticultural disease controller and a method for controlling the diseases
US6194444B1 (en) 1996-09-30 2001-02-27 Nihon Nohyaku Co., Ltd 1,2,3-Thiadiazole derivatives or salts thereof and agrohorticultural disease controller and method for using the same
US6313154B1 (en) 1996-09-30 2001-11-06 Nihon Nohyaku Co., Ltd. Bis-thiadiazole derivatives or salts thereof and agrohorticultural disease controller and method for using the same
WO2001091558A1 (en) * 2000-05-31 2001-12-06 Bayer Aktiengesellschaft Herbicidal agents based on substituted carboxamides
WO2007087906A1 (en) * 2006-02-01 2007-08-09 Bayer Cropscience Sa Fungicide n-cycloalkyl-benzyl-amide derivatives
CN101921244A (en) * 2010-09-02 2010-12-22 南开大学 Derivatives of 4-methyl-1,2,3-thiadiazole containing 4-(1,1,2,2-tetrafluoroethoxy)-3,5-dichloroanilino and their synthetic methods and use
US20110144169A1 (en) * 2003-08-29 2011-06-16 Cuny Gregory D Inhibitors of cellular necrosis
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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4253864A (en) * 1979-07-23 1981-03-03 Monsanto Company Substituted-1,2,3-thiadiazole-safening agents
DE3029375A1 (en) * 1980-07-31 1982-03-04 Schering Ag, 1000 Berlin Und 4619 Bergkamen METHOD FOR PRODUCING 3-ACYLAZOPROPIONIC ACID ESTERS
US4914097A (en) * 1987-02-25 1990-04-03 Mitsubishi Kasei Corporation N-indanyl carboxamide derivative and agricultural/horticultural fungicide containing the derivative as active ingredient
DE3814117A1 (en) * 1988-04-22 1989-11-02 Schering Ag SUBSTITUTED 2-THIADIAZOLYLCARBONYL-CYCLOHEXAN-1,3-DIONE AND THEIR IMINODERIVATIVES, METHODS FOR THE PRODUCTION OF THESE COMPOUNDS AND THEIR USE AS AGENTS WITH HERBICIDES AND PLANT GROWTH REGULATORS
AU626402B2 (en) * 1989-04-19 1992-07-30 Sumitomo Chemical Company, Limited An amide compound and its production and use
US5264448A (en) * 1989-04-19 1993-11-23 Sumitomo Chemical Company, Limited Amide compound and its production and use
DE69813004T2 (en) * 1997-10-31 2003-09-25 Nihon Nohyaku Co., Ltd. THIADIAZOLE CARBOXAMIDE DERIVATIVE, AGENT FOR CONTROLLING PLANT DISEASES AND METHOD FOR USE THEREOF
EP1175834A4 (en) * 1999-04-30 2006-03-01 Nihon Nohyaku Co Ltd METHOD OF USING BACTERICIDE COMPOSITION
EP3034494A1 (en) 2007-08-15 2016-06-22 President and Fellows of Harvard College Heterocyclic inhibitors of necroptosis

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3940407A (en) * 1974-09-16 1976-02-24 Syntex (U.S.A.) Inc. β-Adrenergic blocking agents in the 1,2,3-thiadiazole series

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE795811A (en) * 1972-02-25 1973-08-22 Bristol Myers Co ANTIBACTERIAL AGENTS AND METHOD FOR PREPARING THEM
DD103124A5 (en) * 1972-03-23 1974-01-12
US3874873A (en) * 1972-03-27 1975-04-01 Fmc Corp Herbicidal compositions based on 1,2,3-thiadiazol-5-yl ureas
US3787434A (en) * 1972-03-27 1974-01-22 Fmc Corp Herbicidal 1,2,3-thiadiazol-5-yl ureas
US3776907A (en) * 1972-06-12 1973-12-04 Bristol Myers Co 7-(d-(alpha-amino-alpha-phenyl-,2-thienyl-and 3-thienyl-acetamido))-3-(1,2,3-thiadiazol-4-or 5-yl)-carbonylthiomethyl-3-cephem-4-carboxylic acids
DE2324732C2 (en) * 1973-05-14 1983-06-01 Schering Ag, 1000 Berlin Und 4619 Bergkamen N-phenyl-N'-1,2,3-thiadiazol-5-yl-thiourea, growth-regulating agent containing this compound and a process for its preparation
US4101548A (en) * 1977-02-22 1978-07-18 Bristol-Myers Company 1,2,3-Thiadiazole amides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3940407A (en) * 1974-09-16 1976-02-24 Syntex (U.S.A.) Inc. β-Adrenergic blocking agents in the 1,2,3-thiadiazole series

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Noller, "Chemistry of Organic Compounds", 2nd Edition, p. 161, (1957). *
Pain et al., "J. Chem. Soc.", (1965), pp. 5166-5176. *
Raap et al., "Can. J. Chem.", vol. 46, pp. 1057-1063, (1968). *
Shafiee et al., "J. Het. Chem.", vol. 14, pp. 567-571, (1977). *
Shafiee, "J. Het. Chem.", vol. 13, pp. 301-304, (1976). *

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CN112194642A (en) * 2020-10-20 2021-01-08 浙江工业大学 A kind of 1,2,3-thiadiazole compound and its preparation method and application

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